EP1363958B1 - Preparation de copolymeres d'un monomere de vinyle aromatique et d'un alcool allylique - Google Patents

Preparation de copolymeres d'un monomere de vinyle aromatique et d'un alcool allylique Download PDF

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Publication number
EP1363958B1
EP1363958B1 EP02713537A EP02713537A EP1363958B1 EP 1363958 B1 EP1363958 B1 EP 1363958B1 EP 02713537 A EP02713537 A EP 02713537A EP 02713537 A EP02713537 A EP 02713537A EP 1363958 B1 EP1363958 B1 EP 1363958B1
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Prior art keywords
copolymer
styrene
vinyl aromatic
alcohol
saa
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EP1363958A1 (fr
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Shao-Hua Guo
Wei Wang
Daniel B. Pourreau
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Lyondell Chemical Technology LP
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Arco Chemical Technology LP
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/08—Allyl alcohol

Definitions

  • the invention relates to the preparation of vinyl aromatic-allylic alcohol copolymers.
  • the invention relates to the preparation of copolymers having low molecular weights and low hydroxyl functionality.
  • Styrene-allyl alcohol (SAA) copolymers are known.
  • U.S. Pat. Nos. 2,588,890 and 2,630,430 teach copolymerzing styrene with allyl alcohol in the presence of oxygen as a catalyst.
  • the SAA copolymer thus prepared has high gel content and inferior properties.
  • U.S. Pat. Nos. 2,894,938 and 2,900,359 teach copolymerizing styrene with allyl alcohol using organic peroxides as initiators in the absence of oxygen.
  • the polymerization is conducted in a bulk process by charging allyl alcohol, styrene and an initiator into a reactor and heating the reaction mixture to a polymerization temperature (180°C to 300°C).
  • the SAA copolymer has a low gel content and a functionality greater than 4.
  • U.S. Pat. No. 2,940,946 teaches a semi-batch process for making SAA copolymers. The process is conducted by initially charging allyl alcohol, an initiator, and a portion of styrene into a reactor, and adding the remaining styrene gradually into the reaction mixture during the polymerization.
  • the copolymer has low color and improved thermal stability.
  • U.S. Pat. Nos. 5,444,141 and 5,886,114 teach the preparation of SAA copolymers by initially charging allyl alcohol, a portion of styrene and a portion of an initiator into a reactor and gradually adding the remaining styrene and initiator into the reaction mixture during the polymerization. The process gives substantially higher yields compared with the process disclosed in U.S. Pat. No. 2,940,946.
  • U.S. Pat. No. 6,103,840 teaches an improved process over that of U.S. Pat. No. 5,444,141.
  • the process is conducted by increasing the reaction temperature during the addition of styrene and initiator.
  • the process gives even higher yields of SAA copolymers.
  • U.S. Pat. No. 6,153,713 discloses a process for making a hydroxy-functional acrylic resin comprising copolymerising a C 1 -C 20 alkyl or aryl (meth)acrylate monomer, one or more allyl monomers, optionally an ethylenic monomer, and a hydroxyalkyl(meth)acrylate monomer, in the presence of a free-radical initiator. Said process is advantageously performed in the absence of any reaction solvent.
  • SAA-100 and SAA-101 have been commercially produced for several decades. They have 70/30 and 60/40 molar ratios of recurring units of styrene to allyl alcohol, respectively. Although these SAA copolymers differ in the hydroxyl content or hydroxyl number (OH#, SAA-100: 200 mg KOH/g; SAA-101: 255 mg KOH/g), they have essentially the same hydroxyl functionality (about 5). High hydroxyl functionality of the copolymers gives SAA-based coatings high crosslinking density. However, high functionality also limits the use of the copolymers in many areas, such as in the synthesis of polyester resins where SAA can cause gel formation.
  • SAA-103 which has only about 20 mole % of the recurring units of allyl alcohol (hydroxyl number: 125 mg KOH/g).
  • SAA-103 has even higher hydroxyl functionality (about 7) than SAA-100 or SAA-101. While SAA-103 has a lower concentration of hydroxyl groups, it also has much longer chains, so the number of hydroxyl groups per polymer chain is actually higher than SAA-100 or SAA-101.
  • a new process for producing SAA copolymers is needed. Ideally, the process would produce SAA copolymers having low hydroxyl functionality and low molecular weights.
  • the invention is a process for making copolymers of a vinyl aromatic monomer and an allylic alcohol.
  • the process begins with charging a reactor with an allylic alcohol, 0-50% of the total amount to be used of a vinyl aromatic monomer, 0-100% of the total amount to be used of a free-radical initiator and an organic solvent in an amount greater than or equal to 10% by weight of the total amount of the vinyl aromatic monomer.
  • the reaction mixture is then heated at a temperature within the range of about 100°C to about 185°C.
  • the remaining vinyl aromatic monomer and initiator are added to the reaction mixture at a decreasing rate during the polymerization.
  • a reactor is initially charged with an allylic alcohol.
  • Allylic alcohols useful in the process preferably have the general structure: in which R is selected from hydrogen, a C 1 -C 10 alkyl group, or a C 8 -C 10 aryl group.
  • suitable allylic alcohols are allyl alcohol, methallyl alcohol, and 2-ethyl-2-propen-1-ol. Mixtures of allylic alcohols can be used. Allyl alcohol is preferred because it is commercially available and inexpensive.
  • the amount of allylic alcohol to be used is determined by many factors. They include the desired hydroxyl number of the copolymer, the reaction temperature, the amount of vinyl aromatic monomer to be used, the amount of initiator to be used, and the manner of the addition of the vinyl aromatic monomer and the initiator. Determining how much allylic alcohol to be used is further complicated by the low reactivity of allylic alcohols. Allylic monomers have much lower reactivity than vinyl aromatic monomers. The great disparity in the monomeric reactivities requires a large excess of allylic alcohols in the reaction mixture to achieve an adequate incorporation of allylic alcohols in the copolymer. In general, more than 25% of excess allylic alcohol is needed. The unreacted allylic alcohol is removed from the polymer after polymerization and is reused.
  • the reactor is initially charged with 0-50% of the total amount to be used of a vinyl aromatic monomer.
  • R' is hydrogen or a C 1 to C 10 alkyl group.
  • suitable vinyl aromatic monomers are styrene, ⁇ -methylstyrene, p-methylstyrene, p-t-butylstyrene, 9-vinylanthracene, 2-vinylnaphthalene, and the like, and mixtures thereof. Styrene is particularly preferred.
  • the total amount of vinyl aromatic monomer to be used is determined mainly by the desired copolymer composition. Vinyl aromatic monomers polymerize essentially completely.
  • the remaining vinyl aromatic monomer is gradually added, at a decreasing rate, into the reactor during the course of polymerization. At least 50% of the vinyl aromatic monomer is added to the reaction mixture gradually during the polymerization.
  • the ratio of the vinyl aromatic monomer to allylic alcohol is kept essentially constant so that the copolymer produced has a relatively uniform composition.
  • the process comprises initially charging the reactor with 0-100% of the total amount of a free-radical initiator.
  • Suitable free-radical initiators include peroxides, hydroperoxides, peresters, azo compounds, and many others known to the polymer industry. Examples of suitable free-radical initiators are hydrogen peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl perbenzoate, 2,2'-azobisisobutyronitrile, and the like, and mixtures thereof.
  • the total amount of the initiator to be used is determined by many factors, but mainly by the desired polymerization rate. When more initiator is used, faster polymerization is achieved. Surprisingly, the molecular weight of the copolymer does not vary significantly with the change of the initiator concentration.
  • the process comprises charging the reactor with an organic solvent in an amount greater than or equal to 10% by weight of the total amount of the vinyl aromatic monomer.
  • the solvent is charged initially into the reactor.
  • the solvent is charged partly into the reactor initially, and the remaining is added during the polymerization.
  • the solvent is used in an amount greater than about 20 wt % of the total amount of the vinyl aromatic monomer. More preferably, the amount of solvent is greater than about 50 wt % of the total amount of the vinyl aromatic monomer.
  • Suitable solvents are those in which the copolymer is soluble under the polymerization conditions.
  • C 4 -C 18 linear or cyclic aliphatic hydrocarbons examples include C 4 -C 18 linear or cyclic aliphatic hydrocarbons, C 6 -C 18 aromatic hydrocarbons, esters, ethers, ketones, alcohols, glycol ethers, and the like, and mixtures thereof.
  • suitable solvents are toluene, xylenes, cyclohexane, methyl amyl ketone, butyl acetate, and propylene glycol methyl ether acetate. Toluene and xylenes are preferred.
  • an organic solvent enables the preparation of SAA copolymers having both low molecular weight and low hydroxyl functionality.
  • the polymerization is conducted at a temperature within the range of about 100°C to about 185°C.
  • Increasing temperature reduces the disparity of the monomeric reactivities between the vinyl aromatic monomer and the allylic alcohol, and thus enhances the incorporation of the allylic monomer into the copolymer.
  • increasing temperature also induces high pressure, which increases the risk of the operation.
  • the polymerization is preferably performed under relatively low pressure because allyl alcohol is highly toxic.
  • the polymerization is conducted at a temperature from about 125°C to about 165°C.
  • the invention includes copolymers made by the process.
  • the copolymers differ from those known in the art in that they have lower hydroxyl functionality.
  • the copolymers have an average hydroxyl functionality less than about 4.
  • the copolymers have average hydroxyl functionality from about 1.5 to about 2.5.
  • the copolymers made by the process of the invention not only have low hydroxyl functionality but also have essentially no gel content.
  • gel we mean that the polymer is crosslinked during the polymerization and becomes partially insoluble in the solvent. When a polymer has no gel content, its solution is clear. In addition, the copolymers have much lower solution viscosity than the existing products.
  • the copolymers have a number average molecular weight from about 1,000 to about 3,000 and a molecular weight distribution from about 1.5 to about 5.5.
  • the copolymers preferably have a hydroxyl number from about 30 mg KOH/g to about 150 mg KOH/g.
  • the preferred copolymer made by the process is a styrene-allyl alcohol copolymer.
  • Styrene (250 g) and T-hydro 70 (30 g, 70% aqueous solution of t-butyl hydroperoxide, product of Lyondell Chemical) are mixed, chilled to 5°C, purged with nitrogen, and then charged to the addition pump.
  • the reactor is purged three times with nitrogen, sealed, and the contents are heated to 145°C.
  • the mixture of styrene and initiator is added to the reactor gradually at a decreasing rate over five hours while maintaining the reaction temperature at 145°C.
  • the addition rate is hour 1: 90 g; hour 2: 75 g; hour 3: 60 g; hour 4: 40 g; and hour 5: 15 g.
  • the reaction mixture is kept at 145°C for another 0.5 hour following monomer and initiator addition. Unreacted monomers and solvent are removed by vacuum distillation (maximum temperature: 150°C).
  • the solid SAA copolymer is discharged from the reactor at 25°C.
  • the SAA copolymer has number average molecular weight (Mn) 1800, weight average molecular weight (Mw) 4400, hydroxyl number (OH#) 64.1 mg KOH/g, and Tg: 66°C. It has average hydroxyl functionality (calculated based on Mn and OH#) 2.06.
  • a one-liter stainless-steel reactor equipped as in Example 1 is charged with allyl alcohol (62.5 g), styrene (37 g), di-t-butyl peroxide (7.5 g) and xylenes (175 g). Additional styrene (175 g) and di-t-butyl peroxide (6.7 g) are mixed, chilled to 5°C, purged with nitrogen, and then charged to the addition pump. The reactor is purged three times with nitrogen, sealed, and the contents are heated to 155°C. The mixture of styrene and initiator is added to the reactor gradually at a decreasing rate over eight hours while maintaining the reaction temperature at 155°C.
  • the addition rate is hour 1: 34.7 g; hour 2: 33.0 g; hour 3: 28.8 g; hour 4: 25.2 g; hour 5: 21.0 g; hour 6: 18.4 g; hour 7: 12.7; and hour 8: 7.9 g.
  • the reaction mixture is kept at 155°C for another 0.5 hour following monomer and initiator addition. Unreacted monomers and solvent are removed.
  • the solid SAA copolymer is discharged from the reactor at 25°C.
  • the SAA copolymer has Mn 1910, Mw 3990, OH# 61.8 mg KOH/g, and Tg 65°C. It has average hydroxyl functionality 2.1.
  • Example 2 is repeated, but the polymerization temperature is 145°C rather than 155°C.
  • the SAA copolymer has Mn 2380, Mw 5610, OH# 60.6 mg KOH/g, and Tg 73.8°C. It has average hydroxyl functionality 2.57.
  • Example 2 is repeated, but the reactor is charged with 125 grams, rather than 62.5 grams, of allyl alcohol and the polymerization temperature is 145°C rather than 155°C.
  • the SAA copolymer has Mn 2164, Mw 4690, OH# 94.7 mg KOH/g, and Tg 64.7°C. It has average hydroxyl functionality 3.65.
  • An SAA copolymer is prepared in the absence of a solvent according to the method of U.S. Pat. No. 5,444,141.
  • di-t-butylperoxide (16 g) are charged to a one-liter stainless-steel reactor equipped as in Example 1. After purging three times with nitrogen, the reactor is sealed, and the contents are heated to 145°C.
  • Di-t-butylperoxide (8 g) is mixed with styrene (234 g), and this mixture is pumped into the reactor over seven hours at 145°C at a decreasing rate: hour 1: 50 g; hour 2: 45 g; hour 3: 40 g; hour 4: 35 g; hour 5: 30 g; hour 6: 24 g; and hour 7: 18 g. Heating continues at 145°C for an additional 0.5 hour. Unreacted monomers are removed.
  • the SAA copolymer (322 g) has OH# 199 mg KOH/g, Mn 1500, and Mw 3400. It has hydroxyl functionality 5.3.
  • SAA-103 is prepared in the absence of a solvent according to the method of U.S. Pat. No. 5,886,114.
  • allyl alcohol (1000 g), styrene (353 g), and di-t-butylperoxide (76 g) are charged to a five-liter stainless-steel reactor equipped similarly to Example 1 but separately having a monomer addition pump and an initiator addition pump. After purging three times with nitrogen, the reactor is sealed, and the contents are heated to 145°C.
  • Styrene (1225 g) is charged to the monomer addition pump and di-t-butylperoxide (35.8 g) is charged to the initiator addition pump.
  • Styrene and di-t-butylperoxide are added gradually to the reactor over seven hours at 145°C at decreasing rates.
  • the styrene addition rate is hour 1: 246 g; hour 2: 235 g; hour 3: 207 g; hour 4: 179 g; hour 5: 150 g, hour 6: 129 g, and hour 7: 89 g.
  • the di-t-butyl peroxide addition rate is hour 1: 8.0 g; hour 2: 6.5 g; hour 3: 6.0 g; hour 4: 5.0 g; hour 5: 4.5 g; hour 6: 3.5 g; and hour 7: 2.5 g. Heating continues at 145°C for an additional 0.5 hour. Unreacted monomers are removed.
  • the process of the invention in which a solvent is used, gives SAA copolymers having hydroxyl functionality less than 4 (see Examples 1-4). More interestingly, the process enables us to prepare SAA copolymers that have a hydroxyl functionality of about 2 (see Examples 1-3). In contrast, without the addition of a solvent, the SAA copolymers have a hydroxyl functionalities greater than 4 (see Comparative Examples 5-8).
  • SAA copolymers are dissolved in a variety of solvents listed in Table 2 by 50 wt % of solids. Brookfield viscosity of the solutions is measured at 25°C. As shown in Table 2, the new SAA copolymer of Example 1 has much lower solution viscosity than commercial SAA copolymers. The low solution viscosity makes the new SAA copolymers valuable for ultra-high solids coatings.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Claims (18)

  1. Procédé pour fabriquer un copolymère d'un monomère de vinyle aromatique et d'un alcool allylique, ledit procédé comprenant :
    (a) le chargement d'un réacteur avec un alcool allylique, 0 à 50% de la quantité totale d'un monomère de vinyle aromatique destinée à être utilisée, 0 à 100% de la quantité totale d'un initiateur à radicaux libres destinée à être utilisée, et un solvant organique en une quantité supérieure ou égale à 10% en poids de la quantité totale du monomère de vinyle aromatique,
    (b) le chauffage du mélange réactionnel à une température comprise dans la plage d'environ 100°C à environ 185°C, et;
    (c) l'addition progressive au mélange réactionnel, à une vitesse décroissante, du reste de monomère de vinyle aromatique et de l'initiateur à radicaux libres, dans lequel le copolymère produit a une fonctionnalité hydroxyle moyenne inférieure à 4 environ.
  2. Procédé selon la revendication 1, dans lequel le copolymère a une fonctionnalité hydroxyle comprise dans l'intervalle d'environ 1.5 à environ 2.5.
  3. Procédé selon la revendication 1, dans lequel le monomère de vinyle aromatique est choisi dans le groupe consistant en le styrène, l'α-méthylstyrène, le ρ-méthylstyrène, le ρ-t-butylstyrène et les mélanges de ceux-ci.
  4. Procédé selon la revendication 1, dans lequel l'alcool allylique est choisi dans le groupe consistant en l'alcool d'allyle, l'alcool de méthallyle, et un mélange de ceux-ci.
  5. Procédé selon la revendication 1, dans lequel l'alcool allylique est l'alcool d'allyle.
  6. Procédé selon la revendication 1, dans lequel le monomère de vinyle aromatique est le styrène.
  7. Procédé selon la revendication 1, dans lequel l'alcool allylique est l'alcool d'allyle et le monomère de vinyle aromatique est le styrène.
  8. Copolymère fabriqué selon le procédé de la revendication 1.
  9. Copolymère selon la revendication 8, ayant une valeur de poids moléculaire moyen en nombre comprise dans la gamme d'environ 1000 à environ 3000.
  10. Copolymère selon la revendication 8, ayant une distribution de poids moléculaire comprise dans la gamme d'environ 1,5 à environ 5,5.
  11. Copolymère selon la revendication 8, ayant un indice hydroxyle compris dans l'intervalle d'environ 30 à environ 150 mg KOH/g.
  12. Copolymère selon la revendication 8, dans lequel le monomère de vinyle aromatique est choisi dans le groupe consistant en le styrène, l'α-méthylstyrène, le ρ-méthylstyrène, le ρ-t-butylstyrène et les mélanges de ceux-ci.
  13. Copolymère selon la revendication 8, dans lequel le monomère de vinyle aromatique est le styrène.
  14. Copolymère selon la revendication 8, dans lequel l'alcool allylique est choisi dans le groupe consistant en l'alcool d'allyle et l'alcool de méthallyle.
  15. Copolymère selon la revendication 8, dans lequel l'alcool allylique est l'alcool d'allyle.
  16. Copolymère selon la revendication 8, dont la teneur en gel est par principe nulle.
  17. Procédé pour fabriquer un copolymère de styrène - alcool d'allyle en l'absence d'oxygène, ledit procédé comprenant :
    (a) le chargement d'un réacteur avec de l'alcool d'allyle, 0 à 50% de la quantité totale de styrène destinée à être utilisée, 0 à 100% de la quantité totale d'un initiateur à radicaux libres destinée à être utilisée, et un hydrocarbure aromatique en C6-C18 en une quantité supérieure ou égale à 10% en poids de la quantité totale de styrène.
    (b) le chauffage du mélange réactionnel à une température comprise dans la plage d'environ 100°C à environ 185°C, et;
    (c) l'addition progressive au mélange réactionnel, à une vitesse décroissante, du reste de styrène et de l'initiateur à radicaux libres, dans lequel le copolymère produit a une fonctionnalité hydroxyle moyenne inférieure à 4 environ.
  18. Copolymère de styrène - alcool d'allyle susceptible d'être obtenu par le procédé de la revendication 7, et ayant une fonctionnalité hydroxyle comprise dans l'intervalle d'environ 1,5 à environ 2,5 et dont la teneur en gel est par principe nulle.
EP02713537A 2001-02-14 2002-01-31 Preparation de copolymeres d'un monomere de vinyle aromatique et d'un alcool allylique Expired - Lifetime EP1363958B1 (fr)

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US782900 2001-02-14
US09/782,900 US6455657B1 (en) 2001-02-14 2001-02-14 Preparation of vinyl aromatic-allylic alcohol copolymers
PCT/US2002/003336 WO2002064649A1 (fr) 2001-02-14 2002-01-31 Preparation de copolymeres d'un monomere de vinyle aromatique et d'un alcool allylique

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EP1363958B1 true EP1363958B1 (fr) 2005-03-23

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JP (1) JP2004526824A (fr)
KR (1) KR20040034597A (fr)
CN (1) CN1246350C (fr)
AT (1) ATE291596T1 (fr)
CA (1) CA2434988A1 (fr)
DE (1) DE60203375D1 (fr)
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WO (1) WO2002064649A1 (fr)

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US6930156B2 (en) * 2003-10-22 2005-08-16 Equistar Chemicals, Lp Polymer bound single-site catalysts
US7125939B2 (en) * 2004-08-30 2006-10-24 Equistar Chemicals, Lp Olefin polymerization with polymer bound single-site catalysts
KR102368000B1 (ko) * 2014-07-31 2022-02-25 사빅 글로벌 테크놀러지스 비.브이. 용융 중합된 폴리카보네이트
CN109160964B (zh) * 2018-07-31 2021-04-20 万华化学（宁波）有限公司 一种高分子量聚丙烯醇聚合物及其制备方法和应用

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US2630430A (en) 1948-04-05 1953-03-03 Shell Dev Allyl alcohol-styrene copolymers
US2588890A (en) 1948-04-05 1952-03-11 Shell Dev Allyl alcohol-styrene copolymers
US2900359A (en) 1955-01-10 1959-08-18 Monsanto Chemicals Interpolymers of acrylonitrile, an allyl alcohol and a styrene compound, process of preparing same and coating composition therefrom
US2894938A (en) 1955-01-12 1959-07-14 Monsanto Chemicals Copolymer of a styrene compound and an unsaturated alcohol
US2940946A (en) 1956-09-04 1960-06-14 Shell Oil Co Allyl alcohol-vinyl aromatic copolymers
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US5444141A (en) 1994-07-06 1995-08-22 Arco Chemical Technology, L.P. Process for making vinyl aromatic/allylic alcohol copolymers
US5886114A (en) 1996-10-21 1999-03-23 Arco Chemical Technology, L.P. Process for making vinyl aromatic/allyl alcohol copolymers
US5919874A (en) * 1997-07-28 1999-07-06 Arco Chemical Technology, L.P. Process for making hydroxy-functional acrylic resins having low residual allyl monomer content
EP1091982B1 (fr) 1998-06-01 2004-07-28 ARCO Chemical Technology, L.P. Procede de fabrication de copolymeres allyliques/ethyleniques

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CA2434988A1 (fr) 2002-08-22
DE60203375D1 (de) 2005-04-28
US20020147292A1 (en) 2002-10-10
WO2002064649A1 (fr) 2002-08-22
CN1246350C (zh) 2006-03-22
US6455657B1 (en) 2002-09-24
CN1503813A (zh) 2004-06-09
EP1363958A1 (fr) 2003-11-26
ATE291596T1 (de) 2005-04-15
JP2004526824A (ja) 2004-09-02
KR20040034597A (ko) 2004-04-28
MXPA03007264A (es) 2004-06-30

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